DE19601104A1 - Cosmetic and dermatological sunscreen preparations containing triazine derivatives and alkane carboxylic acids - Google Patents

Abstract

The invention relates to combinations of sunscreen active ingredients comprising 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)-tris-benzoic-acid-tris(2 -ethyl hexyl ester) and branched and/or linear alkane carboxylic acids with chains of 10 to 24 carbon atoms, at least 10 % of said alkane carboxylic acids being present in protonated form.

Description

The present invention relates to cosmetic and dermatological light protection preparations treatments, in particular skin care cosmetic and dermatological light protection additives preparations.

The harmful effect of the ultraviolet part of solar radiation on the skin is well known. During rays with a wavelength that is less than 290 nm (the so-called UVC range), absorbed by the ozone layer in the earth's atmosphere cause rays in the range between 290 nm and 320 nm, the so-called called UVB range, erythema, simple sunburn, or even more or less severe burns.

The narrower range becomes the maximum of the erythema effectiveness of sunlight around 308 nm.

Numerous compounds are known for protecting against UVB radiation, in which it is usually a derivative of 3-benzylidene camphor, 4-aminobenzoic acid, the Cinnamic acid, salicylic acid, benzophenone and also 2-phenylbenzimidazole acts.

Also for the range between about 320 nm and about 400 nm, the so-called UVA Area, it is important to have filter substances available because of that too Rays can cause damage. So it has been proven that UVA radiation to a Damage to the elastic and collagen fibers of the connective tissue leads to what the Skin ages prematurely, and that it is the cause of numerous phototoxic and pho  allergic reactions can be seen. The harmful influence of UVB radiation can be enhanced by UVA radiation.

However, UV radiation can also lead to photochemical reactions, in which case the photochemical reaction products interfere with skin metabolism.

Such photochemical reaction products are predominantly radi potash compounds, e.g. B. hydroxyl radicals. Even undefined radical photopro Products, which are created in the skin itself, can be unreactive due to their high reactivity demonstrate controlled follow-up reactions. But also singlet oxygen, a The non-radical excited state of the oxygen molecule can be caused by UV radiation occur, as do short-lived epoxies and many others. Singlet oxygen for example wise distinguishes itself from the triplet oxygen normally present (radical ground state) from increased reactivity. However exist also excited, reactive (radical) triplet states of the oxygen molecule.

UV radiation also belongs to ionizing radiation. So there is a risk that Ionic species are also formed under UV exposure, which in turn then oxidatively in the biochemical processes are able to intervene.

An advantageous UVB filter is the 4,4 ', 4' '- (1,3,5-triazine-2,4,6-triyltriimino) tris benzoic acid tris (2-ethylhexyl ester), synonym: 2,4,6-tris- [anilino- (p-carbo-2′-1′- hexyloxy)] - 1,3,5-triazine.

This UVB filter substance is sold by BASF Aktiengesellschaft under the Warenbe drawing UVINUL® T 150 and is characterized by good UV absorption properties.

The main disadvantage of this UVB filter is the poor solubility in lipids. Known Solvents for this UVB filter can dissolve a maximum of approx. 15% by weight of this filter sen, corresponding to about 1-1.5% by weight of dissolved and thus active UV filter substance.

It was surprising, however, and the skilled person could not have foreseen that light protective active ingredient combinations of 4,4 ', 4' '- 1,3,5-triazine-2,4,6-triyltriimino) tris tris benzoic acid (2-ethylhexyl ester) and branched and / or unbranched alkane car bonic acids with chain lengths of 10 to 24 carbon atoms, these alkane car at least 10% of bonic acids are present or are present in protonated form help share the state of the art.

The use of branched and / or unbranched alkane carboxylic acids with chain lengths of 10 to 24 carbon atoms, wherein at least 10% of these alkane carboxylic acids are present in protonated form or are present as a solvent, solubilizer or solubilizer for 4,4 ', 4' '- 1,3,5- Triazine-2,4,6-triyltriimino) -tris-benzoic acid-tris (2-ethy (hexyl ester)), especially for the Use in light stabilizers.  

Prerequisite for the usability of the active compound combinations according to the invention for the purposes of the invention is of course the cosmetic or dermatological Harmlessness of the underlying substances.

It is possible according to the invention to use the amounts of 4.4 ', 4' '- 1,3,5-triazine-2,4,6- triyltriimino) tris benzoic acid tris (2-ethylhexyl ester) in cosmetic or dermatological applications double preparations compared to the prior art.

It was also astonishing that by adding alkane carboxylic acids according to the invention Stabilization of solutions of 4,4 ′, 4 ′ ′ - (1,3,5-triazine-2,4,6-triyltriimino) tris- benzoic acid tris (2-ethylhexyl ester) is caused because the latter substance not only poor solubility, but also easily crystallized out of its solution lized. A method for stabilizing solutions is therefore also according to the invention des 4,4 ', 4' '- (1 3,5-triazine-2,4,6-triyltriimino) tris-benzoic acid tris (2-ethylhexyl ester), since characterized in that such solutions have an effective content of fiction moderate alkane carboxylic acids is added.

The combinations which are palmitin as alkane carboxylic acids are particularly preferred contain acid and / or stearic acid and / or isostearic acid and / or eicosanoic acid.

The total amount of 4,4 ′, 4 ′ ′ - (1,3,5-triazine-2,4,6-triyltriimino) tris benzoic acid tris (2-- ethylhexyl ester) in the finished cosmetic or dermatological preparations is advantageously from the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight selected, based on the total weight of the preparations.

The total amount of one or more alkane carboxylic acids according to the invention in the finished cosmetic or the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight, based on the total weight of the preparations.

It is advantageous to use weight ratios of 4.4 ′, 4 ′ ′ - (1,3,5-triazine-2,4,6-triyltriimino) tris- benzoic acid tris (2-ethylhexyl ester) and one or more Al according to the invention can carboxylic acids in the range from 1:10 to 10: 1, preferably 1: 4 to 4: 1 choose.  

Cosmetic and dermatological preparations according to the invention advantageously contain also adheres to inorganic pigments based on metal oxides and / or other Metal compounds which are sparingly soluble or insoluble, in particular the oxides of titanium (TiO₂), zinc (ZnO), iron (e.g. Fe₂O₃), zirconium (ZrO₂), silicon (SiO₂), manganese (e.g. MnO), aluminum (Al₂O₃), cerium (e.g. Ce₂O₃), mixed oxides of corresponding metals and mixtures of such oxides. Especially before Zugges are pigments based on Tip.

It is particularly advantageous in the sense of the present invention, although not necessarily when the inorganic pigments are in hydrophobic form, i.e. that is, they are treated to be water-repellent on the surface. This surface treatment can consist in that the pigments according to known methods with a thin be provided with a hydrophobic layer.

One such method is, for example, that the hydrophobic surfaces layer after a rection

n TiO₂ + m (RO) ₃Si-R ′ → n TiO₂ (surface)

is produced. n and m are stoichiometric para used at will meter, R and R ′ the desired organic residues. For example in analogy to DE- OS 33 14 742 shown hydrophobized pigments are advantageous.

Advantageous TiO₂ pigments are, for example, under the trade names MT 100 T available from TAYCA.

The cosmetic and / or dermatological light protection formulation according to the invention stanchions can be composed as usual and the cosmetic and / or matological light protection, also for the treatment, care and cleaning of the Skin and / or hair and as a make-up product in decorative cosmetics.

The cosmetic and dermatological agents according to the invention are used Preparations in the usual way for cosmetics on the skin and / or the hair sufficient amount applied.  

Such cosmetic and dermatological preparations are particularly preferred, which are in the form of a sunscreen. These can also be advantageous at least one further UVA filter and / or at least one further UVB filter and / or at least one inorganic pigment, preferably an inorganic micro pigment, included.

The cosmetic and dermatological preparations according to the invention can Contain cosmetic auxiliaries, as they usually ver in such preparations be applied, e.g. B. preservatives, bactericides, perfumes, substances for ver prevent foaming, dyes, pigments that have a coloring effect, ver thickeners, moisturizing and / or moisturizing substances, fats, oils, waxes or other usual components of a cosmetic or dermatological formulation tion such as alcohols, polyols, polymers, foam stabilizers, electrolytes, organic Solvents or silicone derivatives.

An additional level of antioxidants is generally preferred. Invention Ge As cheap antioxidants can all for cosmetic and / or dermatological Suitable or customary antioxidants are used.

The antioxidants are advantageously selected from the group consisting of amino acid ren (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. Uro canic acid) and its derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine), carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives vate (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g. Thioredoxin, glulathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, Me thyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, Thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nu kleosides and salts) and sulfoximine compounds (e.g. buthioninsulfoximines, homocy Steinsulfoximin, Buthioninsulfone, Penta-, Hexa-, Heptathioninsulfoximin) in very little compatible doses (e.g. pmol to µmol / kg), also (metal) chelators (e.g. α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g. Ci  tronic acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bili ruby, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their Derivatives (e.g. γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, furfu rylidensorbitol and its derivatives, ubiquinone and ubiquinol and their derivatives, Vit amine C and derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), Tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin, rutinic acid and its derivatives, α- Glycosylrutin, Ferulasäure, Furfurylidenglucitol, Carnosin, Butylhydroxytoluol, Butylhy droxyanisole, Nordihydioguajakarzarzäure, Nordihydroguajaretsäure, Trihydroxytbutyro phenone, uric acid and its derivatives, mannose and its derivatives, zinc and its Derivatives (e.g. ZnO, ZnSO₄) selenium and its derivatives (e.g. selenium methionine), stilbene and their derivatives (e.g. stilbene oxide, trans-stilbene oxide) and the ge according to the invention suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and Lipids) of these active ingredients.

The amount of the aforementioned antioxidants (one or more compounds) in the Preparations are preferably 0.001 to 30% by weight, particularly preferably 0.05- 20 wt .-%, in particular 1-10 wt .-%, based on the total weight of the preparation tung.

If vitamin E and / or its derivatives are the antioxidant (s) advantageous, the respective concentrations of which range from 0.001-10% by weight, based on the total weight of the formulation.

If vitamin A or vitamin A derivatives or carotenes or their derivatives the or the antioxidants are advantageous, their respective concentrations from the Range of 0.001-10% by weight based on the total weight of the formulation choose.

The lipid phase can advantageously be selected from the following group of substances:

• - mineral oils, mineral waxes
• - Oils, such as triglycerides of capric or caprylic acid, but preferably Rizi nut oil;  
• - Fats, waxes and other natural and synthetic fat bodies, preferably Esters of fatty acids with alcohols of low C number, e.g. B. with isopropanol, propy lenglycol or glycerin, or esters of fatty alcohols with lower alkanoic acids C number or with fatty acids;
• - alkyl benzoates;
• - silicone oils such as dimethylpolysiloxanes, diethylpolysiloxanes, diphenylpolysiloxanes and mixed forms of it.

The aqueous phase of the preparations according to the invention optionally contains partial

• - Alcohols, diols or polyols of low C number, and their ethers, preferably Ethanol, isopropanol, propylene glycol, glycerin, ethylene glycol, ethylene glycol mo noethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or -monobutyl ether, diethylene glycol monomethyl or monoethyl ether and analog Products, also low C number alcohols, e.g. B. ethanol, isopropanol, 1,2- Propanediol, glycerol and in particular one or more thickeners, which or which can advantageously be selected from the group Silici dioxide, aluminum silicates, polysaccharides or their derivatives, e.g. B. Hyaluron acid, xanthan gum, hydroxypropylmethyl cellulose, particularly advantageous the group of polyacrylates, preferably a polyacrylate from the group of so mentioned carbopoles, for example carbopoles of types 980, 981, 1382, 2984, 5984, each individually or in combination.

The cosmetic or dermatological sunscreen preparations advantageously contain inorganic pigments, especially micropigments, e.g. B. in amounts of 0.1% by weight up to 30% by weight, preferably in amounts of 0.5% by weight to 10% by weight, in particular but 1% by weight to 6% by weight, based on the total weight of the preparations.

It is advantageous according to the invention, apart from the combinations according to the invention, oil-soluble UVA filters and / or UVB filters in the lipid phase and / or water-soluble UVA Use filters and / or UVB filters in the aqueous phase.

The light protection formulations according to the invention can advantageously further substances Contain zen that absorb UV radiation in the UVB range, the total amount  the filter substances z. B. 0.1% by weight to 30% by weight, preferably 0.5 to 10% by weight, is in particular 1 to 6% by weight, based on the total weight of the preparation to provide cosmetic preparations that protect the skin from the protect the entire range of ultraviolet radiation. You can also sunbathe serve as a means of protection.

The other UVB filters can be oil-soluble or water-soluble. Favorable oil-soluble UVB filter substances are e.g. B .:

• - 3-benzylidene camphor derivatives, preferably 3- (4-methylbenzylidene) camphor, 3- Benzylidene camphor;
• - 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid (2- ethylhexyl) ester, 4- (dimethylamino) benzoic acid amyl ester;
• Esters of cinnamic acid, preferably 4-methoxycinnamic acid (2-ethylhexyl) ester, 4- Isopentyl methoxy cinnamate;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• - Esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di (2-ethylhe xyl) ester.

Advantageous water-soluble UVB filter substances are e.g. B .:

• - Salts of 2-phenylbenzimidazole-5-sulfonic acid such as its sodium, potassium or tri ethanolammonium salt, as well as the sulfonic acid itself;
• - Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxyben zophenone-5-sulfonic acid and its salts;
• - Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-Oxo-bornyldenme thyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidenemethyl) sulfonic acid and their Salts.

The list of other UVB filters mentioned, which in combination with the fiction Moderate combinations of active ingredients should of course not be limiting.

It may also be advantageous to combine the combinations according to the invention with other combinations Combine UVA filters that were previously used in coemetic preparations are included. These substances are preferably derivatives of  Dibenzoylmethane, especially 1- (4'-tert-butylphenyl) -3- (4'-methoxphenyl propane-1,3-dione and 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione. This too Combinations or preparations containing these combinations are opposed state of the invention. The quantities used for the UVB combination can be one be set.

It is also advantageous to combine the active compound combinations according to the invention with further UVA and / or to combine UVB filters.

It is also particularly advantageous to use the active compound combinations according to the invention To combine salicylic acid derivatives, some representatives of which are known, which can also absorb UV radiation. Common UV filters include

The invention also relates to a method for producing the invention ß cosmetic and / or dermatological sunscreen preparations, the result is characterized in that the 4,4 ', 4' '- (1,3,5-triazine 2,4,6-triyltriimino) tris benzoic acid tris (2-ethylhexyl ester) in one or more alkanes carboxylic acids or an oil phase containing alkane carboxylic acids at the same moderate stirring and optionally suspended with heating and desired  if homogenized, if necessary with further lipid components and if appropriate combined with one or more emulsifiers, then the oil phase with the aqueous Phase in which a thickener has optionally been incorporated, and which preferably has about the same temperature as the oil phase, mixed, if desired, homogenized and allowed to cool to room temperature. After cooling len to room temperature, especially if volatile constituents are still present to be worked, repeated homogenization.

The following examples are intended to illustrate the present invention without it restrict. All quantities, parts and percentages are, if not otherwise stated, on the weight and the total amount or on the total amount importance of the preparations.  

example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Example 8

Example 9

Claims (6)

1. Sunscreen active ingredient combinations of 4,4 ', 4' '- (1,3,5-triazine-2,4,6-triyltri imino) -tris-benzoic acid-tris (2-ethylhexyl ester) and branched and / or unbranched Alkane carboxylic acids with chain lengths of 10 to 24 carbon atoms, these Al Canceric acids are at least 10% present in protonated form. 2. Use of branched and / or unbranched alkane carboxylic acids with ket ten lengths of 10 to 24 carbon atoms, these alkane carboxylic acids at least 10% is in protonated form or is present as a solvent or solvent solution mediator or solubilizer for 4,4 ′, 4 ′ ′ - (1,3,5-triazine-2,4,6-triyltriimino) tris tris benzoic acid (2-ethylhexyl ester), in particular for use in sunscreens teln. 3. Combinations according to claim 1 or use according to claim 2, characterized ge characterizes that as further light protection filter substances salicylic acid derivatives from the Group (4-isopropylbenzyl salicylate), (2-ethylhexyl salicylate, octyl salicylate) and or (Ho momenthyl salicylate) can be selected. 4. Combinations according to claim 1 or use according to claim 2, characterized ge indicates that the total amount of 4,4 ′, 4 ′ ′ - (1,3,5-triazine-2,4,6-triyltriimino) tris- tris benzoic acid (2-ethylhexyl ester) in the finished cosmetic or dermatological Preparations in the range of 0.1-10.0% by weight, preferably 0.5-6.0% by weight is selected, based in each case on the total weight of the preparations. 5. Combinations according to claim 1 or use according to claim 2, characterized ge indicates that the total amount of one or more alkane carboxylic acids in the finished cosmetic or dermatological preparations from the range of 0.1-10.0 wt .-%, preferably 0.5-6.0 wt .-% is selected, each based on the Total weight of the preparations. 6. Combinations according to claim 1 or use according to claim 2, characterized ge indicates that weight ratios of 4.4 ′, 4 ′ ′ - (1,3,5-triazine-2,4,6-triyltriimino) tris benzoic acid tris (2-ethylhexyl ester) and one or more alkane carboxylic acids the range from 1:10 to 10: 1, preferably 1: 4 to 4: 1 will.